JP6264552B2 - Method for manufacturing solid oxide fuel cell device - Google Patents

Description

  The present invention relates to a method for manufacturing a solid oxide fuel cell device, and more particularly, to a solid oxide fuel cell device including a current collector that electrically connects a plurality of fuel cells housed in a fuel cell module. It relates to a manufacturing method.

  A solid oxide fuel cell (hereinafter also referred to as “SOFC”) uses an oxide ion conductive solid electrolyte as an electrolyte, attaches electrodes on both sides thereof, and supplies fuel gas on one side, The fuel cell operates at a relatively high temperature by supplying an oxidant gas (air, oxygen, etc.) to the other side.

The solid oxide fuel cell device accommodates a cell array composed of a plurality of fuel cells (cell tubes) in a fuel cell module. In this cell arrangement, a plurality of fuel cells are electrically connected to each other by a current collector. For example, in the fuel cell device described in Japanese Patent Application Laid-Open No. 2008-71711 (Patent Document 1), the upper end portions and the lower end portions of a plurality of fuel cells are respectively inserted into the holes of the electrically insulating support plate, and are electrically conductive. It is fixed to the support plate by a sealing material. Further, the upper end portions and the lower end portions of adjacent fuel cells are connected by a connecting member via a conductive sealing material.
Further, in the fuel cell device described in Japanese Patent Application Laid-Open No. 2008-210805 (Patent Document 2), the upper end portions and the lower end portions of many fuel cells are electrically connected using three current collectors. Has been.

JP 2008-71711 A JP 2008-210805 A

  However, as in the fuel cell device of Patent Document 1, when connecting the end portions of adjacent fuel cells at the both ends of the fuel cells with a connecting member and a sealing material, the number of fuel cells is The electrical connection work of the fuel cells is very troublesome and troublesome.

  On the other hand, in the fuel cell device of Patent Document 2, since the ends of many fuel cells are electrically connected by only three current collectors, the electrical connection work of the fuel cells is facilitated. Specifically, each current collector has a mounting hole for mounting a plurality of corresponding fuel cells, and each mounting hole has a radial shape from the edge of the hole toward the center of the hole. A plurality of elastic pieces extending are formed. For this reason, the edge part of a corresponding fuel cell can be inserted in the some attachment hole of each current collector by pressing each current collector with respect to the cell arrangement | sequence which consists of a some fuel cell. And the some elastic piece of each attachment hole can be made to contact elastically with the outer peripheral surface of the edge part of a corresponding fuel cell. As a result, the work efficiency of the work of attaching the current collector to a large number of fuel cells is greatly improved, and the electrical connection work of the fuel cells is simplified.

  However, the present inventor has found that the current collector as in Patent Document 2 has the following problems. That is, since the fuel cell is made of a ceramic material, the shape (diameter, length, bending, etc.) of each fuel cell varies. For this reason, in the cell arrangement | sequence formed by the several fuel cell, the edge part of each fuel cell will shift | deviate from an ideal position.

  Therefore, even if the current collector is aligned with the cell array, the axial center positions of some of the fuel cells are shifted with respect to the corresponding mounting holes of the current collector. In the mounting operation, the pressing force required to press the current collector against the cell array increases. If the current collector is forcibly pressed against the cell array, the electrode provided on the outer surface of the end portion of the fuel cell may be peeled off by the elastic piece. Such electrode damage adversely affects battery performance and device life.

  In order to facilitate the insertion of a plurality of fuel cells into the current collector and to prevent electrode peeling during insertion, the thickness of the current collector should be reduced to reduce the elastic force of the elastic piece. Good. However, since the current collector and the fuel battery cell are brought into contact with each other using the elastic force of the elastic piece in the fuel cell device of the cited document 2, when the elastic force of the elastic piece is reduced, the current collector and the fuel The electrical connection with the battery cell is lost. That is, when the current collector is thinned to reduce the elastic force of the elastic piece, when the current collector is attached to the cell array and during operation of the fuel cell device, There is a possibility that a part of the plurality of elastic pieces of the mounting hole does not properly contact the fuel cell). In particular, if the elastic piece is exposed to a high temperature (for example, 600 ° C. or more) during operation, the elastic coefficient of the elastic piece is reduced, and the elastic force of the elastic piece may be lost due to recrystallization or the like. This is likely to occur. When conduction failure occurs in some of the elastic pieces, the current concentrates on the elastic pieces that are in contact, so that the current concentrates on a specific fuel cell or a part thereof, and the predetermined battery performance is not exhibited, Product life will be shortened.

  As described above, the current collector structure in the fuel cell device of Patent Document 2 facilitates the operation of attaching the current collector to the cell array, but may damage the electrode of the fuel cell when the current collector is attached, and There has been a problem in that there is a risk of poor conduction between the current collector and the fuel cell at least during operation of the fuel cell device.

  Accordingly, the present invention provides a method for manufacturing a solid oxide fuel cell device having a structure in which a plurality of fuel cells are electrically connected by a current collector, and can prevent damage to the electrodes of the fuel cell and also the fuel cell. It is an object of the present invention to provide a method of manufacturing a solid oxide fuel cell device that can ensure electrical connection between the battery and the current collector.

  In order to solve the above-described problems, the present invention provides a cell array composed of a plurality of fuel cells housed in a fuel cell module, and electrodes formed at end portions of the plurality of fuel cells constituting the cell array. A solid oxide fuel cell device manufacturing method comprising: an electrically connected current collector; and a preparation step for preparing a cell array composed of a plurality of fuel cells, The electrode formed at the end is a porous body made of a porous conductive material that constitutes the fuel electrode or air electrode of the fuel cell, and the preparation process conducts to the electrodes of the plurality of fuel cells. A preparatory step including an application step of applying a conductive adhesive, and an attachment step of attaching the current collector to the cell array, wherein the current collector inserts the ends of the plurality of fuel cells, respectively. Metal with multiple mounting holes Each mounting hole is provided with a plurality of elastic pieces. By pressing the current collector against the cell array, the end of the corresponding fuel cell is inserted into each mounting hole of the current collector. Then, the current collector is attached to the cell array by the elastic force of the elastic piece, and the elastic piece and the fuel cell electrode are attached by an attachment step and an adhesive disposed between the elastic piece and the fuel cell electrode. And an adhesion process for adhering to each other.

  When the current collector is elastically attached to the cell array by pressing the current collector against the cell array and inserting the fuel cell into the mounting holes of the current collector, the manufacturing dimensional accuracy of the fuel cell Therefore, it is necessary to press the current collector against the cell array with a large pressing force. However, forcibly pressing the current collector may damage the fuel cell (particularly the electrode layer). In particular, if the elastic force of the elastic piece provided in the mounting hole of the current collector is large, the elastic piece scratches the outer peripheral surface of the fuel cell when inserted, and damages the electrode layer of the fuel cell.

  In order to avoid such damage of the fuel cell, for example, it is necessary to set the elastic force of the elastic piece to be low by forming the elastic piece with a thin plate material. However, if the elastic force of the elastic piece is low, the elastic piece hits the piece at the time of attachment due to a manufacturing dimensional error of the fuel cell, and there is a possibility that poor conduction occurs between the elastic piece and the electrode from the beginning of manufacture. Also, if the elastic force of the elastic piece is low, the current collector is exposed to a high temperature during the operation of the fuel cell device, and the elastic force of the elastic piece further decreases, causing the elastic piece to hit the piece. There is a possibility that partial conduction failure may occur between the elastic piece and the electrode of the fuel cell.

  Therefore, in the present invention, the cell array preparation step includes an application step of applying a conductive adhesive to the electrode of the fuel cell. Then, after the preparation step, an attachment step of attaching the current collector to the cell array is included. In this attachment step, the current collector is attached to the cell array by the elastic force of the elastic piece. An adhesive is disposed between the elastic piece and the electrode of the fuel cell. In this attachment step, since the elastic piece elastically engages with the electrode via the adhesive layer, the electrode is prevented from being damaged, and the workability of attaching the current collector can be maintained well. Further, the elastic piece of the attached current collector can ensure electrical conduction between the electrode and the electrode through the conductive adhesive layer.

  Furthermore, the present invention includes a bonding step of bonding the elastic piece of the current collector and the electrode of the fuel cell with an adhesive in a state where the current collector is attached to the cell array. Therefore, at the time of manufacture, the elastic piece including the elastic piece that contacts with the electrode can be physically fixed to the electrode with a conductive adhesive. Conduction between the piece and the electrode can be ensured. In addition, since the adhesive force of the adhesive compensates for the decrease in elastic force of the elastic piece during operation, even if the elastic force of the elastic piece disappears, the elastic piece does not move relative to the electrode, A conduction state between the piece and the electrode can be ensured.

  Furthermore, in the present invention, since the electrode of the fuel cell is made of the same porous material as the fuel electrode or the air electrode, the production of the fuel cell can be simplified. In the present invention, in the coating step, the conductive adhesive is applied on the electrode so that the adhesive enters the pores of the electrode or is arranged so as to block the pores of the electrode. For this reason, the electrical conductivity of the electrode itself made of a porous material can be improved. Moreover, since the contact area between the elastic piece and the electrode is substantially increased by filling the pores of the electrode with the conductive adhesive, the electrical resistance between the elastic piece and the electrode can be reduced. It becomes possible. Thus, in this invention, the electrical conductivity between a collector and the electrode of a fuel cell can be improved more.

In the present invention, the adhesive preferably includes a particulate conductive material.
According to the present invention configured as described above, since the adhesive includes the particulate conductive material, the particulate conductive material easily enters the pores of the electrode, and the entire electrode that is a porous body or The electrical conductivity in at least the surface layer portion can be increased. Preferably, the particle size of the conductive material is the same as or smaller than the pore size of the pores of the porous body.

In the present invention, preferably, after the coating step, a densification step of sintering a particulate conductive material of the adhesive to form a densified layer of the adhesive is provided.
According to the present invention configured as described above, the conductive material that has entered the pores of the electrode can be obtained by providing a densification step of sintering the adhesive and densifying the adhesive after the coating step. After being partially molten in the pores, it solidifies. Thereby, since the electrical conduction path within the pores of the electrode is substantially enlarged, the electrode can be a dense interconnector with high conductivity.

In this invention, Preferably, a densification process is performed after an attachment process.
According to the present invention configured as described above, the step of densifying the adhesive layer is performed after the attaching step of attaching the current collector to the cell array, so that the adhesive layer is pressurized by the elastic force of the elastic piece. Thus, the adhesive can be sintered. For this reason, in the part of the adhesive pressurized by the elastic piece, the denseness of the adhesive disposed in the electrical conduction path is increased, and the conductivity can be further increased.

In the present invention, preferably, the bonding step is a step of bonding the elastic piece to the electrode of the fuel cell through the adhesive by sintering the particulate conductive material of the adhesive, and the densification step And the bonding step are performed simultaneously by heating the adhesive.
According to the present invention configured as described above, the bonding step is a step of sintering the particulate conductive material of the adhesive, and between the elastic piece and the electrode, the densification step for increasing the conductivity Since the bonding process for maintaining the connection can be performed in one process, the manufacturing process can be simplified.

In the present invention, preferably, the method for manufacturing an oxide fuel cell device includes a reduction step of reducing the fuel electrode of the fuel cell with a high-temperature reducing gas, and the densification step and the adhesion step are performed at a high temperature in the reduction step. This is performed by sintering the adhesive with a reducing gas.
According to the present invention configured as described above, the densification process and the adhesion process are performed simultaneously by the fuel cell reduction process performed at the final stage of the oxide fuel cell device. In this reduction process, when the oxidized fuel cell is reduced with a high-temperature reducing gas, the adhesive placed in the atmosphere of the high-temperature reducing gas is heated, and the densification process and the adhesion process are executed simultaneously. Can do. For this reason, in this invention, it is not necessary to provide a heating process for exclusive use for a densification process and an adhesion process, and a manufacturing process can be simplified.

  According to the method for manufacturing a solid oxide fuel cell device of the present invention, it is possible to prevent the electrode of the fuel cell from being damaged, and to ensure electrical connection between the fuel cell and the current collector.

1 is an overall configuration diagram showing a solid oxide fuel cell apparatus (SOFC) according to an embodiment of the present invention. It is sectional drawing of the fuel cell storage container incorporated in the solid oxide fuel cell apparatus by one Embodiment of this invention. It is sectional drawing which decomposed | disassembled and showed the main member of the fuel cell storage container incorporated in the solid oxide fuel cell apparatus by one Embodiment of this invention. It is sectional drawing which expands and shows the part of the exhaust concentration chamber incorporated in the solid oxide fuel cell apparatus by one Embodiment of this invention. It is a VV cross section in FIG. (A) It is sectional drawing which expands and shows the lower end part of the fuel cell by which the lower end is made into the cathode, (b) It is sectional drawing which expands and shows the lower end part of the fuel cell by which the lower end is made into the anode is there. It is explanatory drawing of the electrical power collector used for the solid oxide fuel cell apparatus by one Embodiment of this invention. It is explanatory drawing of 1 process in the manufacturing process of the solid oxide fuel cell apparatus by one Embodiment of this invention. It is explanatory drawing of 1 process in the manufacturing process of the solid oxide fuel cell apparatus by one Embodiment of this invention. It is explanatory drawing of the fixing method of the electrical power collector which concerns on 1st Example in the manufacturing process of the solid oxide fuel cell apparatus by one Embodiment of this invention. It is a flowchart of the fixing method of the electrical power collector which concerns on 1st Example. In the solid oxide fuel cell device according to one embodiment of the present invention, it is an explanatory view showing a state where the current collector is fixed to the fuel cell. 5 is a flowchart of a current collector fixing method according to a second example in a manufacturing process of a solid oxide fuel cell device according to an embodiment of the present invention. It is explanatory drawing of the fixing method of the electrical power collector which concerns on 3rd Example in the manufacturing process of the solid oxide fuel cell apparatus by one Embodiment of this invention. It is a flowchart of the fixing method of the electrical power collector which concerns on 3rd Example. It is explanatory drawing of the fixing method of the collector which concerns on the 4th Example in the manufacturing process of the solid oxide fuel cell apparatus by one Embodiment of this invention. It is a flowchart of the fixing method of the electrical power collector which concerns on 4th Example.

Next, a solid oxide fuel cell apparatus (SOFC) according to an embodiment of the present invention will be described with reference to the accompanying drawings.
FIG. 1 is an overall configuration diagram showing a solid oxide fuel cell apparatus (SOFC) according to an embodiment of the present invention. As shown in FIG. 1, a solid oxide fuel cell apparatus (SOFC) 1 according to an embodiment of the present invention includes a fuel cell module 2 and an auxiliary unit 4.

  The fuel cell module 2 includes a housing 6, and a fuel cell storage container 8 is disposed inside the housing 6 via a heat insulating material 7. A power generation chamber 10 is configured inside the fuel cell storage container 8, and a plurality of fuel cell cells 16 are concentrically arranged in the power generation chamber 10. With these fuel cell cells 16, A power generation reaction of air, which is fuel gas and oxidant gas, is performed.

  An exhaust collecting chamber 18 is attached to the upper end of each fuel cell 16. The remaining fuel (off-gas) that is not used in the power generation reaction in each fuel cell 16 is collected in the exhaust collection chamber 18 attached to the upper end, and a plurality of fuel cells 16 provided on the ceiling surface of the exhaust collection chamber 18 are provided. It is discharged from the spout. The fuel that has flowed out is burned by the air remaining in the power generation chamber 10 without being used for power generation, and exhaust gas is generated.

  Next, the auxiliary unit 4 stores a water from a water supply source 24 such as a tap water and uses a filter to obtain pure water, and a water for adjusting the flow rate of the water supplied from the pure water tank. A water flow rate adjustment unit 28 (such as a “water pump” driven by a motor) as a supply device is provided. The auxiliary unit 4 also has a fuel blower 38 (a “fuel pump” driven by a motor) that is a fuel supply device that adjusts the flow rate of a hydrocarbon-based raw fuel gas supplied from a fuel supply source 30 such as city gas. Etc.).

  The raw fuel gas that has passed through the fuel blower 38 is introduced into the fuel cell storage container 8 via the desulfurizer 36 disposed in the fuel cell module 2, the heat exchanger 34, and the electromagnetic valve 35. . The desulfurizer 36 is annularly arranged around the fuel cell storage container 8 and removes sulfur from the raw fuel gas. The heat exchanger 34 is provided to prevent the high temperature raw fuel gas whose temperature has risen in the desulfurizer 36 from flowing directly into the electromagnetic valve 35 and degrading the electromagnetic valve 35. The electromagnetic valve 35 is provided to stop the supply of the raw fuel gas into the fuel cell storage container 8.

  The accessory unit 4 includes an air flow rate adjustment unit 45 (such as an “air blower” driven by a motor) that is an oxidant gas supply device that adjusts the flow rate of air supplied from the air supply source 40.

Further, the auxiliary unit 4 is provided with a hot water production device 50 for recovering the heat of the exhaust gas from the fuel cell module 2. The hot water production apparatus 50 is supplied with tap water, and the tap water is heated by the heat of the exhaust gas and supplied to a hot water storage tank of an external hot water heater (not shown).
Furthermore, the fuel cell module 2 is connected to an inverter 54 that is a power extraction unit (power conversion unit) for supplying the power generated by the fuel cell module 2 to the outside.

Next, the internal structure of the fuel cell storage container built in the fuel cell module of the solid oxide fuel cell device (SOFC) according to the embodiment of the present invention will be described with reference to FIGS.
FIG. 2 is a cross-sectional view of the fuel cell storage container, and FIG. 3 is an exploded cross-sectional view of the main members of the fuel cell storage container.
As shown in FIG. 2, a plurality of fuel cells 16 are concentrically arranged in a space in the fuel cell storage container 8, and a fuel gas supply channel 20 that is a fuel channel so as to surround the periphery thereof. An exhaust gas discharge passage 21 and an oxidant gas supply passage 22 are formed concentrically in order. Here, the exhaust gas discharge channel 21 and the oxidant gas supply channel 22 function as an oxidant gas channel that supplies / discharges the oxidant gas.

  First, as shown in FIG. 2, the fuel cell storage container 8 is a substantially cylindrical hermetic container, and an oxidant gas introduction pipe serving as an oxidant gas inlet for supplying air for power generation is provided on the side surface thereof. 56 and an exhaust gas exhaust pipe 58 for exhaust gas exhaust are connected. Further, an ignition heater 62 for igniting the remaining fuel that has flowed out of the exhaust collecting chamber 18 protrudes from the upper end surface of the fuel cell storage container 8.

As shown in FIGS. 2 and 3, inside the fuel cell storage container 8, an inner cylindrical member 64, which is a power generation chamber constituting member, and an outer cylindrical member in order from the inside so as to surround the periphery of the fuel cell 16. 66, an inner cylindrical container 68 and an outer cylindrical container 70 are arranged. The above-described fuel gas supply flow path 20, exhaust gas discharge flow path 21, and oxidant gas supply flow path 22 are flow paths configured between these cylindrical members and cylindrical containers, respectively, and between adjacent flow paths. Heat exchange takes place at.
That is, the exhaust gas discharge passage 21 is disposed so as to surround the fuel gas supply passage 20, and the oxidant gas supply passage 22 is disposed so as to surround the exhaust gas discharge passage 21. Further, the open space on the lower end side of the fuel cell storage container 8 is closed by a substantially circular dispersion chamber bottom member 72 that constitutes the bottom surface of the fuel gas dispersion chamber 76 that disperses the fuel into each fuel cell 16. .

  The inner cylindrical member 64 is a substantially cylindrical hollow body, and its upper end and lower end are open. A circular first fixing member 63 that is a dispersion chamber forming plate is airtightly welded to the inner wall surface of the inner cylindrical member 64. A fuel gas dispersion chamber 76 is defined by the lower surface of the first fixing member 63, the inner wall surface of the inner cylindrical member 64, and the upper surface of the dispersion chamber bottom member 72. The first fixing member 63 is formed with a plurality of insertion holes 63a through which the fuel battery cells 16 are inserted, and each fuel battery cell 16 is inserted into each insertion hole 63a in the ceramic adhesive. Is bonded to the first fixing member 63. As described above, in the solid oxide fuel cell device 1 of the present embodiment, each member constituting the fuel cell module 2 is filled with the ceramic adhesive in the joint portion between the members constituting the fuel cell module 2 and cured. Are hermetically joined to each other.

  The outer cylindrical member 66 is a cylindrical tube disposed around the inner cylindrical member 64, and is generally similar to the inner cylindrical member 64 so that an annular flow path is formed between the outer cylindrical member 66 and the inner cylindrical member 64. It is formed into a shape. Further, an intermediate cylindrical member 65 is disposed between the inner cylindrical member 64 and the outer cylindrical member 66. The intermediate cylindrical member 65 is a cylindrical tube disposed between the inner cylindrical member 64 and the outer cylindrical member 66, and is modified between the outer peripheral surface of the inner cylindrical member 64 and the inner peripheral surface of the intermediate cylindrical member 65. A portion 94 is configured. An annular space between the outer peripheral surface of the intermediate cylindrical member 65 and the inner peripheral surface of the outer cylindrical member 66 functions as the fuel gas supply channel 20. Therefore, the reforming unit 94 and the fuel gas supply channel 20 receive heat due to heat generation in the fuel cell 16 and combustion of residual fuel at the upper end of the exhaust collecting chamber 18. Further, the upper end portion of the inner cylindrical member 64 and the upper end portion of the outer cylindrical member 66 are hermetically joined by welding, and the upper end of the fuel gas supply channel 20 is closed. Furthermore, the lower end of the intermediate cylindrical member 65 and the outer peripheral surface of the inner cylindrical member 64 are hermetically joined by welding.

  The inner cylindrical container 68 is a cup-shaped member having a circular cross section disposed around the outer cylindrical member 66, and an annular flow path having a substantially constant width is formed between the inner cylindrical container 68 and the outer cylindrical member 66. The side surface is formed in a generally similar shape to the outer cylindrical member 66. The inner cylindrical container 68 is disposed so as to cover the open portion at the upper end of the inner cylindrical member 64. An annular space between the outer peripheral surface of the outer cylindrical member 66 and the inner peripheral surface of the inner cylindrical container 68 functions as the exhaust gas discharge passage 21 (FIG. 2). The exhaust gas discharge passage 21 communicates with the space inside the inner cylindrical member 64 through a plurality of small holes 64 a provided in the upper end portion of the inner cylindrical member 64. Further, an exhaust gas discharge pipe 58 that is an exhaust gas outlet is connected to the lower side surface of the inner cylindrical container 68, and the exhaust gas discharge passage 21 is communicated with the exhaust gas discharge pipe 58.

A combustion catalyst 60 and a sheath heater 61 for heating the combustion catalyst 60 are disposed below the exhaust gas discharge passage 21.
The combustion catalyst 60 is a catalyst filled in an annular space between the outer peripheral surface of the outer cylindrical member 66 and the inner peripheral surface of the inner cylindrical container 68 above the exhaust gas discharge pipe 58. Exhaust gas descending the exhaust gas discharge passage 21 passes through the combustion catalyst 60 to remove carbon monoxide and is discharged from the exhaust gas discharge pipe 58.
The sheath heater 61 is an electric heater attached so as to surround the outer peripheral surface of the outer cylindrical member 66 below the combustion catalyst 60. When the solid oxide fuel cell device 1 is started, the combustion catalyst 60 is heated to the activation temperature by energizing the sheath heater 61.

The outer cylindrical container 70 is a cup-shaped member having a circular cross section disposed around the inner cylindrical container 68, and an annular channel having a substantially constant width is formed between the outer cylindrical container 70 and the inner cylindrical container 68. The side surface is formed in a substantially similar shape to the inner cylindrical container 68. An annular space between the outer peripheral surface of the inner cylindrical container 68 and the inner peripheral surface of the outer cylindrical container 70 functions as the oxidant gas supply channel 22.
Further, an oxidant gas introduction pipe 56 is connected to the lower side surface of the outer cylindrical container 70, and the oxidant gas supply flow path 22 communicates with the oxidant gas introduction pipe 56.

  The dispersion chamber bottom member 72 is a substantially circular dish-like member, and is hermetically fixed to the inner wall surface of the inner cylindrical member 64 with a ceramic adhesive. Thereby, a fuel gas dispersion chamber 76 is formed between the first fixing member 63 and the dispersion chamber bottom member 72. In addition, an insertion tube 72 a for inserting the bus bar 80 (FIG. 2) is provided at the center of the dispersion chamber bottom member 72. The bus bar 80 electrically connected to each fuel cell 16 is drawn out of the fuel cell storage container 8 through the insertion tube 72a. Further, the insertion tube 72 a is filled with a ceramic adhesive, and the airtightness of the fuel gas dispersion chamber 78 is ensured. Further, a heat insulating material 72b (FIG. 2) is disposed around the insertion tube 72a.

  An oxidant gas injection pipe 74 having a circular cross section for injecting air for power generation is attached so as to hang down from the ceiling surface of the inner cylindrical container 68. The oxidant gas injection pipe 74 extends in the vertical direction on the central axis of the inner cylindrical container 68, and each fuel cell 16 is disposed on a concentric circle around it. By attaching the upper end of the oxidant gas injection pipe 74 to the ceiling surface of the inner cylindrical container 68, the oxidant gas supply flow path 22 and the oxidant gas formed between the inner cylindrical container 68 and the outer cylindrical container 70 are formed. An injection pipe 74 is communicated. The air supplied through the oxidant gas supply channel 22 is injected downward from the tip of the oxidant gas injection pipe 74, hits the upper surface of the first fixing member 63, and spreads throughout the power generation chamber 10.

  The fuel gas dispersion chamber 76 is a cylindrical airtight chamber formed between the first fixing member 63 and the dispersion chamber bottom member 72, and each fuel cell 16 is forested on the upper surface thereof. Each fuel cell 16 attached to the upper surface of the first fixing member 63 has an inner fuel electrode communicating with the inside of the fuel gas dispersion chamber 76. The lower end portion of each fuel cell 16 penetrates the insertion hole 63a of the first fixing member 63 and protrudes into the fuel gas dispersion chamber 76, and each fuel cell 16 is fixed to the first fixing member 63 by adhesion. ing.

  As shown in FIG. 2, the inner cylindrical member 64 is provided with a plurality of small holes 64 b below the first fixing member 63. A space between the outer periphery of the inner cylindrical member 64 and the inner periphery of the intermediate cylindrical member 65 is communicated with the fuel gas dispersion chamber 76 through a plurality of small holes 64b. The supplied fuel once rises in the space between the inner circumference of the outer cylindrical member 66 and the outer circumference of the intermediate cylindrical member 65, and then descends in the space between the outer circumference of the inner cylindrical member 64 and the inner circumference of the intermediate cylindrical member 65. Then, it flows into the fuel gas dispersion chamber 76 through the plurality of small holes 64b. The fuel that has flowed into the fuel gas dispersion chamber 76 is distributed to the fuel electrode of each fuel cell 16 attached to the ceiling surface (first fixing member 63) of the fuel gas dispersion chamber 76.

  Further, the lower end portion of each fuel cell 16 projecting into the fuel gas dispersion chamber 76 is electrically connected to the bus bar 80 in the fuel gas dispersion chamber 76, and electric power is drawn out through the insertion tube 72a. The bus bar 80 is an elongated metal conductor for taking out the electric power generated by each fuel battery cell 16 to the outside of the fuel battery cell container 8, and is fixed to the insertion pipe 72 a of the dispersion chamber bottom member 72 via the insulator 78. Has been. The bus bar 80 is electrically connected to a current collector 82 attached to each fuel cell 16 inside the fuel gas dispersion chamber 76. The bus bar 80 is connected to the inverter 54 (FIG. 1) outside the fuel cell storage container 8. The current collector 82 is also attached to the upper end portion of each fuel cell 16 projecting into the exhaust collection chamber 18 (FIG. 4). The current collectors 82 at the upper end and the lower end connect the plurality of fuel cells 16 in parallel electrically, and connect the plurality of sets of fuel cells 16 connected in parallel electrically in series. The both ends of this series connection are connected to the bus bar 80, respectively.

Next, the configuration of the exhaust gas collecting chamber will be described with reference to FIGS. 4 and 5.
4 is an enlarged cross-sectional view showing a portion of the exhaust gas collecting chamber, and FIG. 5 is a VV cross section in FIG.
As shown in FIG. 4, the exhaust concentration chamber 18 is a donut-shaped cross-section chamber attached to the upper end of each fuel cell 16, and an oxidant gas injection pipe 74 is provided at the center of the exhaust concentration chamber 18. Extends through.

  As shown in FIG. 5, three stays 64 c for supporting the exhaust collecting chamber 18 are attached to the inner wall surface of the inner cylindrical member 64 at equal intervals. As shown in FIG. 4, each stay 64 c is a small piece obtained by bending a thin metal plate. By placing the exhaust collection chamber 18 on each stay 64 c, the exhaust collection chamber 18 is concentric with the inner cylindrical member 64. Positioned above. As a result, the gap between the outer peripheral surface of the exhaust collecting chamber 18 and the inner peripheral surface of the inner cylindrical member 64 and the gap between the inner peripheral surface of the exhaust collecting chamber 18 and the outer peripheral surface of the oxidizing gas injection pipe 74 are as follows. , Uniform over the entire circumference (FIG. 5).

The exhaust collecting chamber 18 is configured by hermetically joining the collecting chamber upper member 18a and the collecting chamber lower member 18b.
The aggregation chamber lower member 18b is a circular dish-shaped member opened upward, and a cylindrical portion for allowing the oxidant gas injection pipe 74 to pass therethrough is provided at the center thereof.
The aggregation chamber upper member 18a is a circular dish-shaped member that is open at the bottom, and an opening for allowing the oxidant gas injection pipe 74 to pass therethrough is provided at the center thereof. The aggregation chamber upper member 18a is configured to be fitted into a donut-shaped cross-sectional area opened above the aggregation chamber lower member 18b.

The gap between the inner peripheral surface of the wall around the aggregation chamber lower member 18b and the outer peripheral surface of the aggregation chamber upper member 18a is filled with a ceramic adhesive and cured, so that the airtightness of the joint is ensured. Yes.
Further, a large-diameter seal ring 19a is disposed on the ceramic adhesive layer formed of the ceramic adhesive filled in the joint portion, and covers the ceramic adhesive layer. The large-diameter seal ring 19a is an annular thin plate, is disposed so as to cover the filled ceramic adhesive after being filled with the ceramic adhesive, and is fixed to the exhaust collecting chamber 18 by curing of the adhesive.

  On the other hand, the ceramic adhesive is also filled and hardened between the outer peripheral surface of the cylindrical portion at the center of the aggregation chamber lower member 18b and the edge of the opening at the center of the aggregation chamber upper member 18a. It is secured. Further, a small-diameter seal ring 19b is disposed on the ceramic adhesive layer formed of the ceramic adhesive filled in the joint portion, and covers the ceramic adhesive layer. The small-diameter seal ring 19b is an annular thin plate, is disposed so as to cover the filled ceramic adhesive after being filled with the ceramic adhesive, and is fixed to the exhaust collecting chamber 18 by curing of the adhesive.

  A plurality of circular insertion holes 18c are provided on the bottom surface of the aggregation chamber lower member 18b. The upper end portions of the fuel cells 16 are respectively inserted into the insertion holes 18c, and the fuel cells 16 extend through the insertion holes 18c. A ceramic adhesive is poured onto the bottom surface of the aggregation chamber lower member 18b through which each fuel cell 16 penetrates, and is cured, whereby a gap between the outer periphery of each fuel cell 16 and each insertion hole 18c. Are hermetically filled, and each fuel cell 16 is fixed to the aggregation chamber lower member 18b.

  Further, a circular thin plate-like cover member 19c is disposed on the ceramic adhesive poured on the bottom surface of the aggregation chamber lower member 18b, and is fixed to the aggregation chamber lower member 18b by hardening of the ceramic adhesive. The cover member 19c is provided with a plurality of insertion holes at positions similar to the insertion holes 18c of the aggregation chamber lower member 18b, and the upper end portion of each fuel cell 16 has a ceramic adhesive layer and the cover member 19c. It extends through.

  On the other hand, a plurality of jet outlets 18d for jetting the collected fuel gas are provided on the ceiling surface of the exhaust collecting chamber 18 (FIG. 5). Each ejection port 18d is arranged on the circumference of the aggregation chamber upper member 18a. The remaining fuel that is not used for power generation flows into the exhaust collecting chamber 18 from the upper end of each fuel battery cell 16, and the fuel collected in the exhaust collecting chamber 18 flows out from each jet outlet 18d, where it is burned. The

Next, a configuration for reforming the raw fuel gas supplied from the fuel supply source 30 will be described with reference to FIG.
First, an evaporating portion 86 for evaporating water for steam reforming is provided in the lower portion of the fuel gas supply flow path 20 configured by a space between the inner cylindrical member 64 and the outer cylindrical member 66. . The evaporation unit 86 includes a ring-shaped inclined plate 86 a attached to the lower inner periphery of the outer cylindrical member 66 and a water supply pipe 88. The evaporator 86 is disposed below the oxidant gas introduction pipe 56 for introducing power generation air and above the exhaust gas discharge pipe 58 that discharges exhaust gas. The inclined plate 86 a is a metal thin plate formed in a ring shape, and its outer peripheral edge is attached to the inner wall surface of the outer cylindrical member 66. On the other hand, the inner peripheral edge of the inclined plate 86 a is positioned above the outer peripheral edge, and a gap is provided between the inner peripheral edge of the inclined plate 86 a and the outer wall surface of the inner cylindrical member 64.

  The water supply pipe 88 is a pipe that extends in the vertical direction from the lower end of the inner cylindrical member 64 into the fuel gas supply flow path 20, and the water for steam reforming supplied from the water flow rate adjustment unit 28 passes through the water supply pipe 88. To the evaporation unit 86. The upper end of the water supply pipe 88 passes through the inclined plate 86a and extends to the upper surface side of the inclined plate 86a, and the water supplied to the upper surface side of the inclined plate 86a is the upper surface of the inclined plate 86a and the inner wall surface of the outer cylindrical member 66. Stay between. The water supplied to the upper surface side of the inclined plate 86a is evaporated there to generate water vapor.

A fuel gas introduction part for introducing the raw fuel gas into the fuel gas supply channel 20 is provided below the evaporation part 86. The raw fuel gas sent from the fuel blower 38 is introduced into the fuel gas supply channel 20 via the fuel gas supply pipe 90. The fuel gas supply pipe 90 is a pipe extending vertically from the lower end of the inner cylindrical member 64 into the fuel gas supply flow path 20.
Further, the upper end of the fuel gas supply pipe 90 is positioned below the inclined plate 86a. The raw fuel gas sent from the fuel blower 38 is introduced to the lower side of the inclined plate 86a and rises to the upper side of the inclined plate 86a while the flow path is restricted by the inclination of the inclined plate 86a. The raw fuel gas that has risen to the upper side of the inclined plate 86 a rises together with the water vapor generated in the evaporation section 86.

  A fuel gas supply channel partition wall 92 is provided above the evaporation portion 86 in the fuel gas supply channel 20. The fuel gas supply channel partition wall 92 is an annular metal plate provided so as to vertically separate an annular space between the inner periphery of the outer cylindrical member 66 and the outer periphery of the intermediate cylindrical member 65. A plurality of injection ports 92a are provided at equal intervals on the circumference of the fuel gas supply channel partition wall 92, and the upper space and the lower space of the fuel gas supply channel partition wall 92 are formed by these injection ports 92a. Is communicated. The raw fuel gas introduced from the fuel gas supply pipe 90 and the water vapor generated in the evaporation portion 86 once stay in the space below the fuel gas supply flow path partition wall 92 and then pass through each injection port 92a to become fuel. It is injected into the space above the gas supply channel partition wall 92. When injected from each injection port 92a into a wide space above the fuel gas supply flow path partition wall 92, the raw fuel gas and water vapor are rapidly decelerated and mixed sufficiently here.

  Further, a reforming portion 94 is provided in the upper part of the annular space between the inner periphery of the intermediate cylindrical member 65 and the outer periphery of the inner cylindrical member 64. The reforming part 94 is arranged so as to surround the upper part of each fuel battery cell 16 and the periphery of the exhaust collecting chamber 18 above it. The reforming unit 94 includes a catalyst holding plate (not shown) attached to the outer wall surface of the inner cylindrical member 64 and a reforming catalyst 96 held thereby.

As described above, when the raw fuel gas and water vapor mixed in the space above the fuel gas supply passage partition wall 92 come into contact with the reforming catalyst 96 filled in the reforming unit 94, The steam reforming reaction SR shown in the formula (1) proceeds.
C _m H _n + xH ₂ O → aCO ₂ + bCO + cH ₂ (1)

  The fuel gas reformed in the reforming section 94 flows downward in the space between the inner periphery of the intermediate cylindrical member 65 and the outer periphery of the inner cylindrical member 64, flows into the fuel gas dispersion chamber 76, and each fuel cell. 16 is supplied. Although the steam reforming reaction SR is an endothermic reaction, the heat required for the reaction is supplied by the combustion heat of the offgas flowing out from the exhaust collecting chamber 18 and the heat generated in each fuel cell 16.

Next, the fuel battery cell 16 will be described with reference to FIG.
In the solid oxide fuel cell device 1 according to the embodiment of the present invention, a cylindrical horizontal stripe cell using a solid oxide is adopted as the fuel cell 16. On each fuel cell 16, a plurality of single cells 16a are formed in a horizontal stripe shape, and one fuel cell 16 is configured by electrically connecting them in series. Each fuel cell 16 is configured such that one end thereof is an anode (anode) and the other end is a cathode (cathode), and half of the plurality of fuel cells 16 has an upper end as an anode and a lower end as a cathode. The other half are arranged so that the upper end is a cathode and the lower end is an anode.

  FIG. 6A is an enlarged cross-sectional view showing a lower end portion of the fuel battery cell 16 whose lower end is a cathode, and FIG. 6B is a cross-sectional view of the fuel battery cell 16 whose lower end is an anode. It is sectional drawing which expands and shows a lower end part.

  As shown in FIG. 6, the fuel cell 16 is formed of an elongated cylindrical porous support body 97 and a plurality of layers formed in a horizontal stripe pattern on the outside of the porous support body 97. Around the porous support 97, a fuel electrode layer 98, a reaction suppression layer 99, a solid electrolyte layer 100, and an air electrode layer 101 are formed in a horizontal stripe shape in order from the inside. For this reason, the fuel gas supplied through the fuel gas dispersion chamber 76 flows inside the porous support body 97 of each fuel battery cell 16, and the air injected from the oxidant gas injection pipe 74 is the air electrode. It flows outside the layer 101. Each single cell 16 a formed on the fuel cell 16 is composed of a set of fuel electrode layer 98, reaction suppression layer 99, solid electrolyte layer 100, and air electrode layer 101. The fuel electrode layer 98 of one single cell 16 a is electrically connected to the air electrode layer 101 of the adjacent single cell 16 a via the interconnector layer 102. Thereby, the several single cell 16a formed on the one fuel cell 16 is electrically connected in series.

  As shown in FIG. 6A, an electrode layer 103a is formed on the outer periphery of the porous support 97 at the cathode side end of the fuel battery cell 16, and a lead film layer 104a is formed outside the electrode layer 103a. Has been. At the cathode side end, the air electrode layer 101 and the electrode layer 103a of the single cell 16a located at the end are electrically connected by the interconnector layer 102. The electrode layer 103 a and the lead film layer 104 a are formed so as to penetrate the first fixing member 63 at the end portion of the fuel cell 16 and protrude downward from the first fixing member 63. The electrode layer 103a is formed below the lead film layer 104a, and the current collector 82 is electrically connected to the electrode layer 103a exposed to the outside. As a result, the air electrode layer 101 of the single cell 16a located at the end is connected to the current collector 82 via the interconnector layer 102 and the electrode layer 103a, and current flows as shown by the arrows in the figure. Further, a gap between the edge of the insertion hole 63a of the first fixing member 63 and the lead film layer 104a is filled with a ceramic adhesive, and the fuel cell 16 is fixed first on the outer periphery of the lead film layer 104a. It is fixed to the member 63.

As shown in FIG. 6B, at the anode side end of the fuel battery cell 16, the fuel electrode layer 98 of the single cell 16a located at the end is extended, and the extension of the fuel electrode layer 98 is the electrode. It functions as the layer 103b. A lead film layer 104b is formed outside the electrode layer 103b.
The electrode layer 103 b and the lead film layer 104 b are formed so as to penetrate the first fixing member 63 at the end portion of the fuel cell 16 and protrude downward from the first fixing member 63.
The electrode layer 103b is formed below the lead film layer 104b, and the current collector 82 is electrically connected to the electrode layer 103b exposed to the outside. As a result, the fuel electrode layer 98 of the single cell 16a located at the end is connected to the current collector 82 via the electrode layer 103b formed integrally, and a current flows as shown by an arrow in the figure. Further, a gap between the edge of the insertion hole 63a of the first fixing member 63 and the lead film layer 104b is filled with a ceramic adhesive, and the fuel cell 16 is fixed on the outer periphery of the lead film layer 104b. It is fixed to the member 63.

  6A and 6B, the configuration of the lower end portion of each fuel cell 16 has been described, but the configuration of the upper end portion of each fuel cell 16 is also the same. In the upper end portion, each fuel cell 16 is fixed to the aggregation chamber lower member 18b of the exhaust aggregation chamber 18, but the configuration of the fixed portion is the same as the fixing to the first fixing member 63 in the lower end portion. .

Next, the structure of the porous support body 97 and each layer is demonstrated.
In the present embodiment, the porous support body 97 is formed by extruding and sintering a mixture of forsterite powder and a binder.
In this embodiment, the fuel electrode layer 98 is a conductive thin film composed of a mixture of NiO powder and 10YSZ (10 mol% Y ₂ O ₃ -90 mol% ZrO ₂ ) powder.

In the present embodiment, the reaction suppression layer 99 is a thin film composed of a cerium-based composite oxide (LDC 40, that is, 40 mol% La ₂ O ₃ -60 mol% CeO ₂ ). The chemical reaction between the layer 98 and the solid electrolyte layer 100 is suppressed.
In the present embodiment, the solid electrolyte layer 100 is a thin film made of LSGM powder having a composition of La _0.9 Sr _0.1 Ga _0.8 Mg _0.2 O ₃ . Electric energy is generated by the reaction between oxide ions and hydrogen or carbon monoxide through the solid electrolyte layer 100.

In this embodiment, the air electrode layer 101 is a conductive thin film made of powder having a composition of La _0.6 Sr _0.4 Co _0.8 Fe _0.2 O ₃ .
In this embodiment, the interconnector layer 102 is a conductive thin film made of SLT (lanthanum-doped strontium titanate). Adjacent single cells 16 a on the fuel cell 16 are connected via the interconnector layer 102.
The electrode layers 103a and 103b are formed of the same material as the fuel electrode layer 98 in the present embodiment.
In this embodiment, the lead film layers 104a and 104b are made of the same material as that of the solid electrolyte layer 100.

Note that the lead film layers 104a and 104b are the same dense layers as the solid electrolyte layer 100, and can be hermetically sealed by being bonded to a ceramic adhesive.
In the present embodiment, the electrode layers 103a and 103b are formed of the same porous material as that of the fuel electrode layer 98. However, the electrode layers 103a and 103b are not limited to this, and the reaction suppression layer 99 or the air electrode layer. It may be formed of another electrically conductive porous material including the same porous material as that of 101. For example, the air electrode layer 101 of the single cell 16a formed at a position closest to the end of the fuel cell 16 may be further extended in the end direction, and the extended portion may be used as an electrode layer.

Next, the current collector will be described with reference to FIG.
FIG. 7 is a view of the current collector 82 as viewed from above. FIGS. 7A and 7B show current collectors 82A and 82B attached to the upper end and lower end of the fuel cell 16, respectively. FIG. 7C is an enlarged view of the attachment hole 84 formed in the current collectors 82A and 82B.

The current collector 82 is formed by machining a thin plate material having elasticity and conductivity. In this embodiment, it is formed using a nickel plate.
The current collector 82A includes two substantially semicircular current collector plates 83a and 83b. The current collector 82A has a substantially circular outer shape by arranging these current collector plates 83a and 83b adjacent to each other, and a circular opening for inserting the oxidant gas injection pipe 74 in the central portion. It is formed.

  The current collector 82B includes one substantially semicircular current collector plate 83c and two substantially quadrant current collector plates 83d and 83e. The current collector 82B has a substantially circular outer shape by arranging these current collector plates 83c to 83e adjacent to each other, and a circular opening is formed in the central portion. The current collector plates 83d and 83e are provided with connection portions 83f and 83g for connecting the bus bar 80.

  In the present embodiment, a plurality (76 in this example) of fuel cells 16 are divided into four groups of 19 cells. Then, as shown in FIG. 2, when the current collector 82 is connected to the upper end portion and the lower end portion of the fuel battery cell 16, the fuel battery cells 16 of each group are connected in parallel via the current collector 82. Four groups are connected in series. That is, for example, if the current collector plate 83d connected to one bus bar 80 is an anode (anode), the current collector plate 83a is connected via the first group of fuel cells 16 connected to the current collector plate 83d. The lower half is the cathode (cathode), the upper half is the anode, and the left half of the current collector plate 83c is the cathode via the second group of fuel cells 16. Similarly, the right half of the current collector plate 83c serves as an anode, the upper half of the current collector plate 83b serves as a cathode and the lower half serves as an anode via the third group of fuel cells 16, and finally the fourth group of fuel. A current collecting plate 83e connected to the other bus bar 80 via the battery cell 16 serves as a cathode.

  As shown in FIG.7 (c), the attachment hole 84 of each current collecting plate is formed by radial cutting by machining. One mounting hole 84 is formed by six cut lines. An imaginary line 84b connecting both ends of the cut line forms a circle larger than the outer dimension (imaginary line 84c) of the fuel cell 16. Twelve elastic pieces 84a are formed by the cut lines so as to extend from the virtual line 84b (that is, the inner peripheral edge of the mounting hole 84) in the center direction of the circle (inward in the radial direction).

  Each elastic piece 84a has a substantially sector shape that tapers toward the tip, and the tip can be elastically bent with respect to the base end (virtual line 84b). Therefore, when the fuel cell 16 is inserted into the mounting hole 84, the tip of the elastic piece 84 a comes into contact with the outer peripheral surface of the fuel cell 16 and bends along the outer peripheral surface. Engage elastically. When the fuel cell 16 is inserted to a predetermined position with respect to the current collector plate, the current collector plate is held by the fuel cell 16 by the elastic force of the elastic piece 84a.

Next, with reference to FIG.1 and FIG.2, the effect | action of the solid oxide fuel cell apparatus 1 is demonstrated.
First, in the starting process of the solid oxide fuel cell device 1, the fuel blower 38 is started, fuel supply is started, and energization to the sheath heater 61 is started. When energization of the sheath heater 61 is started, the combustion catalyst 60 disposed above the sheath heater 61 is heated, and the evaporator 86 disposed inside is also heated. The fuel supplied by the fuel blower 38 flows from the fuel gas supply pipe 90 into the fuel cell storage container 8 through the desulfurizer 36, the heat exchanger 34, and the electromagnetic valve 35. The inflowed fuel rises to the upper end in the fuel gas supply flow path 20, then descends in the reforming portion 94, and flows into the fuel gas dispersion chamber 76 through the small hole 64 b provided in the lower part of the inner cylindrical member 64. To do. Immediately after the solid oxide fuel cell device 1 is started, the temperature of the reforming catalyst 96 in the reforming unit 94 has not risen sufficiently, so that fuel reforming is not performed.

  The fuel gas that has flowed into the fuel gas dispersion chamber 76 flows into the exhaust collection chamber 18 through the inside (fuel electrode side) of each fuel cell 16 attached to the first fixing member 63 of the fuel gas dispersion chamber 76. Immediately after the start of the solid oxide fuel cell device 1, the temperature of each fuel cell 16 has not risen sufficiently, and power is not taken out to the inverter 54. Does not occur.

  The fuel that has flowed into the exhaust aggregation chamber 18 is ejected from the ejection port 18 d of the exhaust aggregation chamber 18. The fuel ejected from the ejection port 18d is ignited by the ignition heater 62 and burned there. Due to this combustion, the reforming section 94 disposed around the exhaust aggregation chamber 18 is heated. Further, the exhaust gas generated by the combustion flows into the exhaust gas discharge passage 21 through the small hole 64 a provided in the upper part of the inner cylindrical member 64. The high-temperature exhaust gas descends in the exhaust gas discharge passage 21 and is used for power generation that flows in the fuel gas supply passage 20 provided on the inside and the oxidant gas supply passage 22 provided on the outside. Heat the air. Further, the exhaust gas passes through the combustion catalyst 60 disposed in the exhaust gas discharge passage 21 to remove carbon monoxide and is discharged from the fuel cell storage container 8 through the exhaust gas discharge pipe 58.

  When the evaporation section 86 is heated by the exhaust gas and the sheath heater 61, the water for steam reforming supplied to the evaporation section 86 is evaporated and steam is generated. The water for steam reforming is supplied by the water flow rate adjusting unit 28 to the evaporation unit 86 in the fuel cell storage container 8 through the water supply pipe 88. The water vapor generated in the evaporation unit 86 and the fuel supplied via the fuel gas supply pipe 90 are temporarily retained in the space below the fuel gas supply flow path partition wall 92 in the fuel gas supply flow path 20. The fuel gas is supplied from a plurality of injection ports 92 a provided in the fuel gas supply channel partition wall 92. The fuel and water vapor that are vigorously injected from the injection port 92 a are sufficiently mixed by being decelerated in the space above the fuel gas supply flow path partition wall 92.

  The mixed fuel and water vapor rise in the fuel gas supply channel 20 and flow into the reforming unit 94. In a state where the reforming catalyst 96 of the reforming unit 94 has risen to a temperature at which reforming can be performed, when the fuel / steam mixture passes through the reforming unit 94, a steam reforming reaction occurs, and the mixture Is reformed into a fuel rich in hydrogen. The reformed fuel flows into the fuel gas dispersion chamber 76 through the small hole 64b. A large number of small holes 64 b are provided around the fuel gas dispersion chamber 76, and a sufficient volume is secured as the fuel gas dispersion chamber 76, so that the reformed fuel protrudes into the fuel gas dispersion chamber 76. Evenly flows into the battery cells 16.

  On the other hand, the air, which is the oxidant gas supplied by the air flow rate adjusting unit 45, flows into the oxidant gas supply passage 22 through the oxidant gas introduction pipe 56. The air flowing into the oxidant gas supply channel 22 rises in the oxidant gas supply channel 22 while being heated by the exhaust gas flowing inside. The air rising in the oxidant gas supply passage 22 is collected at the center at the upper end portion in the fuel cell storage container 8 and flows into the oxidant gas injection pipe 74 communicated with the oxidant gas supply passage 22. To do. The air flowing into the oxidant gas injection pipe 74 is injected into the power generation chamber 10 from the lower end, and the injected air hits the upper surface of the first fixing member 63 and spreads throughout the power generation chamber 10. The air that has flowed into the power generation chamber 10 flows into the gap between the outer peripheral wall of the exhaust collecting chamber 18 and the inner peripheral wall of the inner cylindrical member 64, and between the inner peripheral wall of the exhaust collecting chamber 18 and the outer peripheral surface of the oxidizing gas injection pipe 74. Ascend through the gaps in between.

  At this time, a part of the air flowing through the outside (air electrode side) of each fuel cell 16 is used for the power generation reaction. Further, a part of the air that has risen above the exhaust aggregation chamber 18 is used for the combustion of fuel ejected from the ejection port 18d of the exhaust aggregation chamber 18. Exhaust gas generated by the combustion and air remaining without being used for power generation and combustion flow into the exhaust gas discharge passage 21 through the small hole 64a. The exhaust gas and air that have flowed into the exhaust gas discharge passage 21 are discharged after carbon monoxide is removed by the combustion catalyst 60.

  In this way, the temperature rises to about 650 ° C., which is the temperature at which each fuel cell 16 can generate electricity, and the reformed fuel flows inside each fuel cell 16 (fuel electrode side) and outside (air electrode side). When air flows through the chamber, an electromotive force is generated by a chemical reaction. In this state, when the inverter 54 is connected to the bus bar 80 drawn out from the fuel cell storage container 8, electric power is taken out from each fuel cell 16 to generate power.

  Further, in the solid oxide fuel cell device 1 of the present embodiment, the power generation air is injected from the oxidant gas injection pipe 74 disposed in the center of the power generation chamber 10, and the inside of the power generation chamber 10 is exhausted. Ascending through the uniform gap between the chamber 18 and the inner cylindrical member 64 and the uniform gap between the exhaust collecting chamber 18 and the oxidant gas injection pipe 74. For this reason, the air flow in the power generation chamber 10 is almost completely axisymmetric, and the air flows uniformly around each fuel cell 16. Thereby, the temperature difference between each fuel cell 16 is suppressed, and an equal electromotive force can be generated in each fuel cell 16.

Next, an outline of a manufacturing process of the solid oxide fuel cell device 1 according to the embodiment of the present invention will be described with reference to FIGS.
First, the inner cylindrical member 64, the intermediate cylindrical member 65, the outer cylindrical member 66, and the first fixing member 63 are assembled together by welding (see FIG. 3). Further, the reforming catalyst 94 is filled in the reforming section 94 provided between the inner cylindrical member 64 and the intermediate cylindrical member 65. Further, the water supply pipe 88 and the fuel gas supply pipe 90 are also attached by welding.

Next, one end of the fuel cell 16 is inserted into the insertion hole 63a of the first fixing member 63, and the fuel cell 16 is positioned with respect to the first fixing member 63 by a jig or the like. Next, an aggregation chamber lower member 18b, which is a second fixing member, is disposed on the other end side of the positioned fuel battery cell 16.
Thus, in the state where each fuel cell 16 is positioned, the ceramic adhesive is injected onto the aggregation chamber lower member 18b, the cover member 19c is disposed, and then heated in a drying furnace, thereby the ceramic adhesive. To cure. As a result, a ceramic adhesive layer 118 (see FIG. 2) is formed. By the ceramic adhesive layer 118, the cell joint portion between the fuel battery cell 16 and the aggregation chamber lower member 18b is airtightly joined.
Each fuel cell 16 is bonded to the lead film layers 104a and 104b with a ceramic adhesive (see FIG. 6).

In the heating process of the ceramic adhesive, the temperature in the drying furnace is raised from room temperature to about 60 ° C. in about 120 minutes, then raised to about 80 ° C. in about 20 minutes, and then about 80 ° C. for about 60 minutes. Maintained. After maintaining the temperature of about 80 ° C., the temperature in the drying furnace is returned to room temperature in about 30 minutes.
By this heating process, the ceramic adhesive is cured to a state where a subsequent manufacturing process can be performed. In the subsequent process, the ceramic adhesive is cured to a state that can withstand the temperature rise in the starting process of the solid oxide fuel cell device 1 by performing the second heating process.

  Next, the assembly is turned upside down, a ceramic adhesive is injected onto the first fixing member 63 from which the tip of each fuel cell 16 protrudes, and the cover member 67 is disposed. The ceramic adhesive is cured by performing the heating step. Thereby, the ceramic adhesive bond layer 122 (refer FIG. 2) is formed. The cell bonding portion between the fuel cell 16 and the first fixing member 63 is airtightly bonded by the ceramic adhesive layer 122.

  Next, as shown in FIG. 8, a current collector 82 is attached to the front end portion (lower end portion when not vertically inverted) of each fuel cell 16 protruding from the first fixing member 63. Body 82 is connected to bus bar 80. The current collector 82 is positioned so that each attachment hole 84 is positioned above the corresponding fuel cell 16 in the axial direction with respect to the cell array composed of the plurality of fuel cells 16. The current collector 82 is pressed against the cell array from above with a predetermined pressing force. As a result, the end of the fuel cell 16 is inserted into each mounting hole 84, and the current collector 82 is attached to the cell array by the elastic force of the elastic piece 84 a of the mounting hole 84.

  Next, the dispersion chamber bottom member 72 is attached to the assembly. Further, a ceramic adhesive is filled in an annular gap between the outer peripheral surface of the dispersion chamber bottom member 72 and the inner peripheral surface of the inner cylindrical member 64. Further, an insulator 78 is disposed in an insertion tube 72a provided at the center of the dispersion chamber bottom member 72, and is filled with a ceramic adhesive. Each bus bar 80 extending from the current collector 82 passes through the insulator 78 and the ceramic adhesive. In this state, the above-described heating process is performed on the assembly to cure the ceramic adhesive.

  Next, as shown in FIG. 9, the assembly is turned upside down, and a current collector 82 is attached to the tip of each fuel cell 16 fixed so as to protrude from the aggregation chamber lower member 18 b. Further, the aggregation chamber upper member 18a is disposed on the aggregation chamber lower member 18b, and a ceramic adhesive is injected into the gap between the aggregation chamber upper member 18a and the aggregation chamber lower member 18b. A large-diameter seal ring 19a and a small-diameter seal ring 19b are disposed on the ceramic adhesive. In this state, the above heating process is performed on the assembly to form the ceramic adhesive layers 120a and 120b (see FIG. 4).

  Next, the inner cylindrical container 68 and the outer cylindrical container 70 are attached to the assembly by welding or ceramic adhesive. Thereafter, the gap between the outer cylindrical member 66 and the inner cylindrical container 68 is filled with a ceramic adhesive, and is cured by the heating process described above. After this heating step, a second heating step is performed in which the temperature is raised to a higher temperature (for example, about 650 ° C.), and each ceramic adhesive layer is cured to a state that can withstand the temperature increase in the startup step.

Through the above steps, the assembly shown in FIG. 2 is manufactured, and finally a reduction step is performed. In this reduction process, a high-temperature reducing gas (fuel gas, that is, hydrogen gas) is supplied from a fuel gas supply pipe 90 in a high-temperature (for example, about 650 ° C.) furnace, and the reducing gas is used as fuel for each fuel cell 16. Pass through the pole side. Thereby, the fuel electrode oxidized in the atmosphere of the high temperature reducing gas can be reduced, and for example, nickel oxide contained in the fuel electrode can be reduced to nickel.
The reduction step may be performed after returning the assembly to a low temperature after the second heating step described above, or may be performed continuously following the second heating step, or both steps. May be executed simultaneously.

Next, a method for fixing the current collector 82 to the cell array of the fuel cells 16 in the manufacturing process of the solid oxide fuel cell device 1 according to the embodiment of the present invention will be described in detail.
First, the first embodiment will be described with reference to FIGS.
FIG. 10 is an explanatory diagram of a method of fixing the current collector, FIG. 11 is a flowchart of the fixing method, and FIG. 12 is an explanatory diagram showing a state where the current collector is fixed to the fuel cell.
Each fuel cell 16 has a cylindrical porous support 97, and on its outer peripheral surface, a fuel electrode layer 98, a reaction suppression layer 99, a solid electrolyte layer 100, an air electrode layer 101, electrode layers 103a and 103b, Lead film layers 104a and 104b are formed (see FIG. 6).

  First, as shown in FIG. 10A, a conductive adhesive 151 is applied to the exposed surfaces of the electrode layers 103a and 103b at both ends of each fuel cell 16 (step S1 in FIG. 11). This adhesive application step is performed before the plurality of fuel cells 16 are modularized into a cell array, that is, each fuel cell 16 is in a single state.

  The adhesive 151 in the present embodiment is obtained by mixing a solid powder 151b with a binder component 151a, and is in a paste form before curing. As the binder component, for example, any of α-terpineol, a nonionic surfactant, a mixture of polyvinyl butyral and polyacetal can be used. The solid powder is a particulate conductive material that is sintered at or below the operating temperature (for example, about 600 ° C. or higher) of the solid oxide fuel cell device 1, and is, for example, a nickel powder. The average particle size of the powder is set to be equal to or smaller than the pore size of the electrode layer that is a porous body. The powder according to this embodiment has a particle size of about μm to several tens of μm. Therefore, in the adhesive application step, a part of the binder component 151a and the solid powder 151b of the adhesive 151 enters the pores of the electrode layer that is a porous body, or closes the openings of the pores of the electrode layer. Are arranged as follows.

  Next, as shown in FIG. 10B, the adhesive 151 is heated to dry the binder component 151a (step S2 in FIG. 11). In this drying step (first curing step), for example, the fuel cell 16 is disposed in an atmosphere of about 80 ° C. in the drying furnace in the same manner as the heating step described above, thereby drying the binder component 151a. Can do. The drying temperature in the drying step can be set to be equal to or lower than the temperature at which the fixed powder 151b is sintered, although the binder component 151a can be dried. In addition, the heating process of the above-mentioned ceramic adhesive may also serve as this drying process.

In the drying step, the binder component 151a is dried, so that the electrode protective layer 152 mainly composed of the solid powder 151b is formed in the entire pores of the electrode layer or in the pores close to the surface (electrode protective layer). Forming step).
The electrode protective layer 152 of the present embodiment is a layer made mainly of fine nickel powder and harder than the electrode layer. And the electrode protective layer 152 can protect an electrode layer from the external force with respect to an electrode layer by covering an electrode layer.

  Next, by fixing the fuel cell 16 in which the electrode protection layer 152 is formed in a state of being positioned on the first fixing member 63 and the aggregation chamber lower member 18b (see FIG. 8), The resulting cell array is modularized (step S3 in FIG. 11).

  Next, as shown in FIG. 10 (c), a current collector attaching step for attaching the current collectors 82 to both ends of the modularized fuel cell 16 is performed (step S 4 in FIG. 11). Specifically, as indicated by phantom lines in FIG. 10C, the current collector plates 83a to 83e of the current collector 82 are positioned with respect to the cell array. That is, the current collector plates are arranged so that the center of the mounting hole 84 of the current collector 82 is positioned on the substantially axial center of the corresponding fuel cell 16. Then, as shown by a solid line in FIG. 10C, the current collector plate 82 is pressed against the cell array. Thereby, each fuel cell 16 is inserted into the corresponding mounting hole 84. At this time, the plurality of elastic pieces 84 a of the attachment hole 84 are elastically bent along the outer peripheral surface of the fuel cell 16 and come into contact with the outer peripheral surface. When each current collecting plate is pushed into a predetermined position, the elastic piece 84 a is elastically engaged with the electrode protection layer 152. Thereby, the elastic piece 84a and the electrode protective layer 152 are electrically connected.

  When the current collector 82 is attached to the cell array, the current collector 82 moves to a predetermined position while the bent elastic piece 84a contacts the electrode protective layer 152 formed on the outer peripheral surface of the fuel cell 16. To do. At this time, since the electrode layer of the fuel battery cell 16 is covered with the electrode protection layer 152, it is protected from damage due to contact with the elastic piece 84a. Therefore, in this embodiment, the current collector 82 including the elastic piece 84a having a large elastic force can be used.

  Next, as shown in FIG. 10D, an adhesion process (second curing process) for bonding the elastic piece 84a and the electrode protection layer 152 is performed (step S5 in FIG. 11). Specifically, the electrode protective layer 152 is heated at a temperature equal to or lower than the melting point of the solid powder 151b to sinter the solid powder 151b. Due to the sintering, the volume of the electrode protective layer 152 shrinks and becomes dense. This sintering process may be performed only for the adhesion between the current collector 82 and the fuel battery cell 16, but the second heating process or the reducing process of the ceramic adhesive described above performs the sintering process. It can also be combined. If the second heating step or the reduction step is configured to also serve as the sintering step, the manufacturing step can be shortened.

  In this embodiment, nickel powder is used as the solid powder 151b. For this reason, the solid powder 151b is gradually sintered from about 250 ° C., and is completely sintered while the temperature is raised to about 550 ° C. Therefore, in the second heating step or reduction step also serving as the sintering step, for example, the sintering step can be completed in the process of gradually raising the temperature to about 650 ° C.

  On the other hand, in the present embodiment, the current collector 82 is formed of a nickel plate, and when the temperature of the current collector 82 increases, the elastic coefficient of the plate material decreases and recrystallization occurs, resulting in an elastic force. May decrease. When the elastic modulus is lowered or the elastic force is lowered by recrystallization, the pressing force of the elastic piece 84a against the electrode protective layer 152 is lowered, and the contact between the elastic piece 84a and the electrode protective layer 152 may be lost. The recrystallization temperature of nickel is about 530 ° C to about 660 ° C.

  However, in the present embodiment, while the nickel plate material of the current collector 82 has elasticity, the current collector 82 and The material of the solid powder 151b included in the adhesive 151 is selected. Specifically, in this embodiment, the particle size of the solid powder 151b is set so that the solid powder 151b is sintered before the current collector 82 is recrystallized. Therefore, the elastic piece 84 can be bonded to the electrode protective layer 152 in the sintering step.

  Furthermore, in this embodiment, since the electrode protective layer 152 is formed on the surface of the electrode layer before the current collector mounting step, the electrode layer is scratched by the elastic piece 84a when the current collector is mounted. It is possible to prevent damage (peeling). For this reason, the current collector 82 having the elastic piece 84a having a relatively large elastic force can be used. That is, the current collector 82 can be formed from a plate material having a relatively large thickness. When the elastic force of the elastic piece 84a is large, the elastic piece 84a has a relatively large elasticity even when the fuel cell 16 and the current collector 82 are exposed to a high temperature during operation of the solid oxide fuel cell 1. Can hold power. Thereby, even when there is no adhesive force of the electrode protective layer 152 by performing an adhesion | attachment process, the elastic piece 84a can engage with an electrode layer with the elastic force, and can maintain an electrical connection.

  In the sintering step, when the solid powder 151b is heated, at least the surface portion of the solid powder 151b has fluidity and is in a partially molten state. At this time, since the elastic piece 84a presses the electrode protective layer 152 by elastic force, the tip of the elastic piece 84a partially sinks or is buried in the electrode protective layer 152. When the sintering is completed, the fluidity of the solid powder 151b is lost and a solid state is obtained. The electrode protective layer 152 exhibits an adhesive function by changing from a fluid state to a solid state. Thus, when the electrode protective layer 152 is sintered, the elastic piece 84a is firmly bonded to the sintered electrode protective layer 152 as shown in FIG. This prevents the elastic piece 84a from being physically displaced with respect to the electrode layer when an external load such as stress or heat is applied to the elastic piece 84a during operation. Therefore, the electrical conductivity between the current collector 82 and the cell array is ensured via the conductive electrode protective layer 152.

  Thus, in the sintering step, the elastic piece 84a partially sinks in or is covered with the adhesive (electrode protective layer 152), thereby increasing the contact area between the elastic piece 84a and the adhesive, The degree of adhesion between the two becomes strong, and the electrical resistance between the elastic piece 84a and the electrode layer can be reduced.

  In the present embodiment, the manufacturing process is simplified by forming the electrode layers 103 a and 103 b from the same porous material as the fuel electrode layer 98 or the air electrode layer 101. For this reason, since the electrode layer has a porous structure, there is a possibility that the electrical conductivity is not so good or the contact resistance is increased. However, in this embodiment, since the electrode protective layer 152 is formed not only on the surface of the electrode layer but also at least in the pores of the surface layer of the electrode layer, the electrical conductivity of the electrode layer is improved and the electrode protective layer is also improved. The electric resistance between 152 and the electrode layer can also be reduced, and a more efficient fuel cell can be configured.

Furthermore, since the electrode protective layer 152 is sintered, the solid powder 151b that has entered the pores of the electrode layer having a porous structure is partially melted and then solidified and densified. The electrical conduction path at is substantially enlarged. Thereby, a dense interconnector structure with high conductivity can be formed.
Furthermore, since the electrode protection layer 152 is pressed by the elastic piece 84a in the densification process in the sintering process, the density of the electrode protection layer 152 at the location where the elastic piece 84a presses the electrode layer is enhanced. Thereby, the electrical conductivity in the electrical conduction path near the elastic piece 84a can be further increased.
Furthermore, in this embodiment, since the bonding process also serves as a densification process, the manufacturing process can be simplified.

  In addition, when the adhesive application process is executed after modularizing the plurality of fuel cells 16 into a cell arrangement, the adhesive application process is a laborious operation. However, in the present embodiment, the adhesive application step and the binder drying step can be performed on the single fuel cell 16 before the modularization step. For this reason, in this embodiment, work is not troublesome and the manufacturing process can be simplified.

  In this embodiment, the electrode protective layer 152 also serves as an adhesive. However, the present invention is not limited to this, and the elastic piece 84a is further added to the electrode protective layer 152 by further using an adhesive different from the electrode protective layer 152. You may adhere | attach firmly. The use of another adhesive is effective when the adhesion function by the electrode protection layer 152 is not sufficient or when the electrode protection layer 152 does not have the adhesion function.

Next, a second embodiment of the current collector fixing method will be described with reference to FIG.
As described above, in the first embodiment, an adhesive application process and a binder drying process are performed on each fuel battery cell 16 before the modularization process for modularizing the plurality of fuel battery cells 16 into a cell array. However, you may perform an adhesive agent coating process and a binder drying process with respect to a cell arrangement | sequence after a modularization process.

That is, in the second embodiment, as shown in FIG. 13, a modularization process (step S11), an adhesive application process (step S12), a binder drying process (step S13), a current collector mounting process (step S14), The bonding process (step S15) is sequentially performed.
By comprising in this way, since it becomes possible to perform a binder drying process simultaneously with the heating process of a ceramic adhesive agent, it becomes possible to aim at shortening of a manufacturing process and energy saving.

Next, with reference to FIG.14 and FIG.15, 3rd Example about the fixing method of a collector is described.
In the third embodiment, first, a plurality of fuel cells 16 are modularized into a cell arrangement as shown in FIG. 8 (step S21 in FIG. 15).
Next, as shown in FIG. 14A, a conductive adhesive 151 is applied to the surfaces of the electrode layers 103a and 103b (step S22 in FIG. 15). In this adhesive application step, the paste adhesive 151 is applied thicker on the surface of the electrode layer. The adhesive 151 is composed of a binder component 151a and a conductive solid powder 151b, and is the same as that of the embodiment shown in FIG.
However, it is preferable that the adhesive 151 has such a viscosity that it can remain on the electrode layer after application so that it can be applied thickly. For this reason, in the third embodiment, a conductive adhesive different from the embodiment of FIG. 10 may be used as the adhesive 151.

  Next, as shown in FIG. 14 (b), the current collector plates 83a-83e of the current collector 82 are aligned with the cell arrangement (see the phantom lines in FIG. 14 (b)), and each current collector plate Is pushed into the cell array (step S23 in FIG. 15). Thereby, each fuel cell 16 is inserted into the corresponding mounting hole 84. When each current collecting plate is pushed to a predetermined position, the elastic piece 84a of the mounting hole 84 is positioned on the side of the electrode layers 103a and 103b of the fuel cell 16 (see the solid line in FIG. 14B).

  The fuel battery cell 16 is made of a ceramic material and is difficult to form with high dimensional accuracy. For this reason, variations in length, diameter, bending, etc. occur between the plurality of fuel cells 16. For this reason, even if the current collector 82 is aligned with the cell array, the attachment holes 84 may be displaced with respect to the corresponding fuel cells 16. Therefore, when the current collector 82 is temporarily attached to the cell array in the current collector mounting step (step S23), there is a possibility that some of the elastic pieces 84a do not come into contact with the surface of the electrode layer. For example, the right elastic piece 84a in FIG. 14B is in contact with the surface of the electrode layer, but the left elastic piece 84a is not in contact with the surface of the electrode layer.

  For this reason, in the adhesive application process (step S22), the adhesive 151 is applied thicker on the surface of the electrode layer in consideration of the dimensional error of the fuel cell 16. Accordingly, in the current collector mounting step, the elastic piece 84a that does not contact the surface of the electrode layer can be in a state of being buried in the adhesive 151 or in a state of being in contact with at least the adhesive 151.

Next, as shown in FIG. 14C, the adhesive 151 is heated to dry the binder component 151a (step S24 in FIG. 15). This drying process is the same as the drying process described with reference to FIG.
By this drying step, the elastic piece 84a on the right side of FIG. 14C is partially covered with the electrode protection layer 152 made of the solid powder 151b and fixed to the electrode layer in a state in contact with the surface of the electrode layer. On the other hand, the elastic piece 84a on the left side in FIG. 14C is not in contact with the surface of the electrode layer, but is fixed to the electrode layer via the electrode protective layer 152.

Next, as shown in FIG. 14D, an adhering process for adhering the elastic piece 84a and the electrode protective layer 152 is performed (step S25 in FIG. 15). This adhesion process is the same as the drying process described in relation to FIG.
By this bonding step, the elastic piece 84a is firmly bonded to the electrode layer. And since the elastic piece 84a on the right side of FIG. 14 (d) is adhered to the electrode layer by the electrode protection layer 152 while being in contact with the surface of the electrode layer, conduction is ensured by direct contact with the electrode layer. Is done. On the other hand, the elastic piece 84a on the left side of FIG. 14D is not in contact with the surface of the electrode layer, but is adhered to the electrode layer through the electrode protective layer 152, so that the conductive electrode protective layer 152 is provided. Therefore, conduction with the electrode layer can be ensured.

As described above, in the third embodiment, the dimensional error of the fuel battery cell 16 is relatively large, and even after some of the elastic pieces 84a are not in contact with the electrode layer after the current collector mounting step, the fuel cell 16 is surely secured. In addition, all the elastic pieces 84a can be electrically connected to the electrode layer.
Further, when the current collector 82 is heated to the operating temperature during the operation of the solid oxide fuel cell device 1, even if the elastic force of the elastic piece 84a of the current collector 82 is reduced, the elasticity is increased by adhesion. Since the displacement of the piece 84a with respect to the electrode layer is prevented, the conduction between the elastic piece 84a and the electrode layer can be ensured by the electrode protective layer 152.

Next, with reference to FIG.16 and FIG.17, 4th Example about the fixing method of a collector is described.
In the fourth embodiment, first, a plurality of fuel cells 16 are modularized into a cell array as shown in FIG. 8 (step S31 in FIG. 17).
Next, as shown in FIG. 16 (a), the current collector plates 83a-83e of the current collector 82 are aligned with the cell array (see the phantom lines in FIG. 16 (a)), and each current collector plate. Is pushed into the cell array (step S32 in FIG. 17). Thereby, each fuel cell 16 is inserted into the corresponding mounting hole 84. When each current collecting plate is pushed to a predetermined position, the elastic piece 84a of the mounting hole 84 is elastically engaged with the electrode layers 103a and 103b of the fuel cell 16 (see the solid line in FIG. 16A).

Next, as shown in FIG. 16 (b), an adhesive 153 is applied between each elastic piece 84a and the electrode layers 103a and 103b (step S33 in FIG. 17), the adhesive 153 is cured, and the elastic piece 84a is bonded to the electrode layer (step S34 in FIG. 17).
Note that the adhesive 153 may be the conductive adhesive used in Example 1, or may be another conductive adhesive. In this case, after the current collector mounting step (step S32), even if some of the elastic pieces 84a and the electrode layer are not in contact with each other, conduction can be ensured through the adhesive 153.
Further, as the adhesive 153, an adhesive having no conductivity may be used. In this case, after the current collector mounting step, at least the elastic piece 84a in contact with the electrode layer can ensure conduction between the elastic piece 84a and the electrode layer.

Further, in the present embodiment, when the current collector 82 is heated to the operating temperature during operation of the solid oxide fuel cell device 1, the elastic force of the elastic piece 84a of the current collector 82 is reduced. The electrical connection between the elastic piece 84a and the electrode layer can be ensured by the adhesive 153.
As described above, since the dimensional error of the fuel cell 16 is relatively large, even if the current collector plate is aligned with the cell arrangement in the current collector mounting step (step S32), There is a risk that the corresponding fuel cell 16 will shift. For this reason, it is necessary to press the current collector plate against the cell array with a relatively large pressing force. However, if the current collector plate is forcibly pressed, the exposed electrode layers 103a and 103b may be damaged by the elastic piece 84a. (For example, peeling of the electrode layer). In order to prevent such damage, it is conceivable to form the current collector 82 with a thinner plate so as to reduce the elastic force of the elastic piece 84a. However, if the elastic force is reduced, when the current collector 82 is exposed to a high temperature during operation of the solid oxide fuel cell device 1, the elastic force of the elastic piece 84a further decreases, and the elastic piece 84a and Contact with the electrode layer may be lost.

  Therefore, in the fourth embodiment, by fixing the elastic piece 84a and the electrode layer with the adhesive 153, the elastic piece 84a is prevented from being displaced from the electrode layer, so that the non-contact with the electrode layer at high temperature is prevented. Can be prevented. For this reason, it is possible to use the current collector 82 having the elastic piece 84a whose elastic force is set to be small. By forming the current collector 82 from a thinner plate material, the manufacturing cost can be reduced. Can be achieved.

DESCRIPTION OF SYMBOLS 1 Solid oxide type fuel cell apparatus 2 Fuel cell module 4 Auxiliary machine unit 16 Fuel cell 16a Single cell 18 Exhaust collection chamber 18a Aggregation chamber upper member 18b Aggregation chamber lower member 63 First fixed member 80 Bus bar 82 Current collector 82A- 82B Current collector 83a-83e Current collector plate 84 Mounting hole 84a Elastic piece 84b Virtual wire 97 Porous support 98 Fuel electrode layer 99 Reaction suppression layer 100 Solid electrolyte layer 101 Air electrode layer 102 Interconnector layers 103a, 103b Electrode layer 104a 104b Lead film layer 151 Adhesive 151a Binder component 151b Solid powder 152 Electrode protective layer 153 Adhesive

Claims (6)

A cell array composed of a plurality of fuel cells housed in a fuel cell module, and a current collector electrically connected to electrodes formed at end portions of the plurality of fuel cells constituting the cell array. A method for producing a solid oxide fuel cell device comprising:
A preparation step for preparing a cell array composed of a plurality of fuel cells, wherein an electrode formed at an end of the fuel cell is a porous conductive material constituting a fuel electrode or an air electrode of the fuel cell A porous body made of a material, and the preparation step includes an application step of applying a conductive adhesive to the electrodes of the plurality of fuel cells, and
A mounting step for mounting the current collector to the cell array, wherein the current collector is a metal plate in which a plurality of mounting holes for inserting the end portions of the plurality of fuel cells are respectively formed. Each mounting hole is provided with a plurality of elastic pieces, and by pressing the current collector against the cell array, the end of the corresponding fuel cell unit is attached to each mounting hole of the current collector. Inserting and attaching the current collector to the cell array by elastic force of the elastic piece; and
Adhering step of bonding the elastic piece and the electrode of the fuel cell by the adhesive disposed between the elastic piece and the electrode of the fuel cell,
A method for producing a solid oxide fuel cell device, comprising:   The method for manufacturing a solid oxide fuel cell device according to claim 1, wherein the adhesive includes a particulate conductive material.   3. The solid according to claim 2, further comprising a densification step of forming a densified layer of the adhesive by sintering the particulate conductive material of the adhesive after the applying step. A manufacturing method of an oxide fuel cell device.   The method for manufacturing a solid oxide fuel cell device according to claim 3, wherein the densification step is performed after the attachment step. The bonding step is a step of bonding the elastic piece to the electrode of the fuel cell via the adhesive by sintering the particulate conductive material of the adhesive.
5. The method for manufacturing a solid oxide fuel cell device according to claim 4, wherein the densification step and the bonding step are performed simultaneously by heating the adhesive. 6. The manufacturing method of the oxide fuel cell device includes a reduction step of reducing the fuel electrode of the fuel cell with a high-temperature reducing gas,
6. The solid oxide fuel cell device according to claim 5, wherein the densification step and the adhesion step are performed by sintering the adhesive with a high-temperature reducing gas in the reduction step. Manufacturing method.

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